Page 20 THE VELIGER Vol. 6; Supplement half of the ctenidium do not noticeably alter chemore¬ result in appreciable change of chemoreceptive abilities ception. The osphradium functions as an olfactory organ of T. funebralis. and is capable of detecting the presence of an extract containing 2.6 X 10“ parts by wet weight of tube feet LITERATURE CITED from Pisaster ochraceus. The osphradium, when stimu¬ lated, seems to cause the animals to be more sensitive FEDER, H. to stimulations of the head tentacles and epipodial struc¬ 1956. Natural history of Pisaster ochraceus. Doctoral diss., tures. Removal of part of the osphradium does not Stanford Univ. Identification and Location of Carbohydrases in the Intestinal Tract of Tegula funebralis (Mollusca : Gastropoda) WARREN R. BERRIE AND MITCHEL W. DEVEREAUX Hopkins Marine Station of Stanford University. Pacific Grove, California (6 Tables) SINCE Tegula funebralis (A. ADAMS, 1854) is an herbi- parts: buccal cavity, salivary glands, esophagus, stomach vorous marine animal, it is quite evident that it must and digestive gland (since it was impossible to separate have an efficient and well developed carbohydrate diges the stomach from the digestive gland), digestive gland tive mechanism. Although this subject has been explored (portions freed from the stomach), spiral caecum, thin to some degree already (GALLI, 1956), there still seemed hindgut, and thick hindgut. much to be investigated. We limited our efforts to the The purpose of the first experiment was to determine study of five carbohydrates present in the environment the site of enzyme production. The gut segments were of the animal: starch, laminarin, alginate, fucoidin, and excised from snails fresh from the field. These tissues cellobiose. Using these materials we hoped to localize the were refrigerated so as to retard any loss of enzyme points of enzyme production within the alimentary canal activity due to denaturation or autolysis. Pools of tissue and sites of carbohydrate digestion. The extent to which from five animals were washed, weighed, and extracted intracellular and extracellular digestion is involved in the in a tissue grinder equipped with a Teflon pestle (Van foregut and hindgut was also studied. Waters and Rogers Inc., Catalogue no. 48652) with either The substrates were: starch (Baker and Adamson, a citrate-phosphate buffer, pH 5.8, or a phosphate buffer. reagent grade), alginate (Kelco Co., commercial grade), pH 7.4. These buffers were chosen since they approximate cellobiose (Pfanstiehl Chemical Co., C. P grade). Lamin¬ the extremes of hydrogen ion concentration occurring in arin and fucoidin were isolated from Fucus by the the digestive tract. Enzyme activity was determined by method of BLACK, DEWAR, & WOODWARD (1951 - 1952). incubating an appropriate aliquot of tissue extract with The alimentary canal was divided into eight anatomical one of the substrates and assaying for reducing sugar by Page 21 Vol. 6; Supplement THE VELIGER the Somogyi reaction as modified by GALLI (1956). Table 2 Enzyme and substrate controls were incubated simulta¬ Enzyme Controls neously. Incubation was at 15° C for 24 hours. Tissue extracts (w/v) : buccal cavity, 0.42% ; salivary The results are recorded in Tables 1, 2, and 3. It glands, 0.03%; esophagus, 0.06%; stomach and digestive appears that throughout the entire length of the digestive gland, 0.21% ; digestive gland, 0.04%; spiral caecum, tract there is widespread production of large concentra¬ 0.05%; thin hindgut, 0.06%; thick hindgut, 0.07%; tions of amylase and cellobiase. On the other hand, citrate-phosphate buffer, 0.05M, pH 5.8; phosphate there was only a small and localized production of buffer, O.1M, pH 7.4; incubated at 15° C for 24 hours. enzymes that split the 1,4-ß-p-mannuronic acid linkage of algininic acid, the 1,2-a-L-fucose-4-sulfate linkage of uug Reducing Sugar' Tissue fucoidin, and the 1,3-ß-n-glucose linkage of laminarin. pH 5.8 The results would further indicate that the salivary glands buccal cavity 19.0 do not play an important role in enzyme production with the exception of cellobiase. It is also evident from salivary gland 92.3 Table 3 that some of the enzymes show different pH esophagus 19.5 stomach and optima. digestive gland digestive gland Table 1 spiral caecum 18.0 Substrate Controls thin hindgut Substrates, 0.1%; citrate-phosphate buffer, 0.5M, pH 5.8; thick hindgut 82.0 phosphate buffer, O.1M, pH 7.4; incubation at 15° C pH 7.4 for 24 hours. 48.5 buccal cavity ug Reducing Sugar Substrate salivary gland esophagus pH 5.8 stomach and 70.4 starch digestive gland laminarin digestive gland 21.0 alginate spiral caecum fucoidin thin hindgut 312.0 cellobiose thick hindgut pH 7.4 reducing sugar present in 1 mg dry weight of tissue. starch laminarin buccal cavity through the mouth, and into the thick alginate hindgut through the anus. The ligated snails were held at fucoidin 15° C for 24 hours submerged in Millipore filtered sea 474.0 cellobiose water. The snails survived this period of incubation. At ug reducing sugar present in 1 ml substrate the end of the incubation period, the ligated areas were excised, homogenized, and assayed for reducing sugar. A duplicate experiment was performed in which a The second experiment was conducted to investigate mixture of antibiotics was incorporated with the substrate the site of enzyme action. The snails were starved unti in order to assess the role played by intestinal bacteria in the digestive tract was cleared of material. A period of carbohydrate hydrolysis. The antibiotic mixture con¬ about ten days was required. Ligatures were used to tained: 50 units/ml penicillin, 25 ug/ml streptomycin, isolate the previously mentioned parts of the digestive 25 ug/ml terramycin, 5 ug/ml polymixin tract. The results of these experiments are shown in Tables The salivary glands were cut away since they could not 4 and 5. A comparison of Tables 3 and 4 reveals some be excluded by ligatures. It was impossible to make any further points of interest. The salivary glands and esoph- type of ligation between the stomach and digestive gland. agus contain a large amount of cellobiase; yet the absence Ligatures were of nylon thread. Substrate was injected of cellobiose hydrolysis in the esophagus suggests that through the wall into the ligated part with the aid of a 26-gauge needle. The substrate was injected into the the enzymes do not act upon the glucose-B-1,4-glucose Page 22 Vol. 6; Supplement THE VELIGER Table 3 Reducing Sugar Released by Enzyme Action Substrates, 0.1%; citrate-phosphate buffer, O.05M, pH 5.8; phosphate buffer, O.1M, pH 7.4; incubation at 15° C for 24 hours. Anatomical Region Substrates Starch Laminarin Alginate Fucoidin Cellobiose ug Reducing Sugar pH 5.8 buccal cavity 52.5 136.6 53.1 119.0 salivary gland 1988.0 esophagus 49.5 207. 872.7 1008.5 stomach and 322.5 38.5 341.0 digestive gland digestive gland 131.5 spiral caecum 1206.0 105.0 2310.7 406.0 thin hindgut 1888.0 thick hindgut 1698.0 63.4 61.0 46.5 1953.0 pH 7.4 buccal cavity 430.5 161.4 183.3 212.5 salivary gland 746.0 esophagus 107.6 293.7 stomach and 525.6 529.6 digestive gland digestive gland 2164.9 113.0 834.0 spiral caecum 2142.0 thin hindgut 710.0 1504.0 thick hindgut 689.4 434.8 ug reducing sugar released by enzyme extracted from 1 mg dry weight of tissue. The values in the table have been corrected by subtraction of substrate and enzyme controls (see tables 1 and 2). linkages in this portion of the digestive tract. A compar¬ in the lumen or in the wall of the foregut and hindgut. Carbohydrates were again injected into the various seg ison of Tables 4 and 5 shows that antibiotics decrease ments after ligation, and the snails were incubated for 24 carbohydrate hydrolysis and suggests that microorganisms are, in part, involved in the breakdown of carbohydrates hours. The areas were excised, opened, and washed with in all parts of the digestive tract. Hydrolysis of starch and distilled water. Both the washings and a homogenate of cellobiose was most markedly affected by antibiotics. the tissue were then tested for reducing sugar. The results presented in Table 6 suggest that the major- Bacteria were cultured from the foregut and hindgut. The medium used contained: 1% agar, 0.001% aqueous ity of cellobiose hydrolysis in the hindgut occurred in the wall. Such a simple interpretation is not possible. The extract of snail, 0.001% yeast extract, 0.01% Difco pep¬ test procedure only determined the amounts of reducing tone, and 0.05% of one of the carbohydrate substrates and was buffered at one of the two different pH's — 5.8 sugar present in lumen and tissue. Cellobiose is a reducing or 7.4. A variety of colonial types developed. Hydrolysis sugar itself. An adequate correction for the reducing activity of the substrate when it is possibly divided of starch by the organisms was detected by loss of a between tissue and lumen is not possible. Since hydrolysis reaction with iodine. The presence of reducing sugars of this disaccharide does not result in a great change in could be demonstrated in the other cultures by Tollen's molecular size, no marked difference in the absorption of Reagent. Splitting of cellobiose could not be determined the substrate and products of its hydrolysis might be by these methods. The purpose of the final set of experiments was to expected. No distinction between intracellular digestion and absorption of the products of digestion can be made determine whether carbohydrate hydrolysis was occurring Page 23 Vol. 6; Supplement THE VELIGER Table 4 Reducing Sugars Released in Situ Substrates, 0.1% ; incubation at 15°C for 24 hours Substrates Anatomical Region Starch Laminarin Alginate Fucoidin Cellobiose ug Reducing Sugar 193.5 1965.0 240.0 220.3 321.5 buccal cavity & salivary gland 155.5 113.5 170.0 buccal cavity 249.5 182.3 esophagus 105.5 103.4 65.7 282.6 521.6 1032.6 stomach and 873.6 digestive gland 2680.0 296.0 289.2 1113.0 849.3 spiral caecum 132.0 1772.8 thin hindgut 416.0 152.7 172.1 1594.7 thick hindgut 1660.0 63.9 ug reducing sugar corrected by subtraction of appropriate tissue and substrate controls. Table 5 Reducing sugar released in Situ in the Presence of an Antibiotic Substrates, 0.1% ; incubation at 15° C for 24 hours. Substrates Anatomical Region Starch Laminarin Alginate Fucoidin Cellobiose ug Reducing Sugar 1760.4 180.6 190.0 buccal cavity & 253.7 salivary gland 87.5 145.0 buccal cavity 107.5 0 esophagus 169.3 stomach and 184.6 155.8 digestive gland 132.6 466.0 228.5 spiral caecum 208.5 135.6 242.0 120.8 154.0 430.7 thin hindgut 307.0 112.2 63.9 14130 thick hindgut ug reducing sugar corrected by subtraction of appropriate tissue and sub- strate controls. and are then carried to the hindgut in an active form. in the case of this small molecular weight substrate. The GALLI (1956), evidently, did not expect the hindgut to results with starch, on the other hand, do indicate be important in digestion since he ignored this organ in appreciable intracellular digestion in the hindgut tissue. his studies. Yet the activity of the hindgut was clearly demonstrated in our experiments. Also, when GALLI DISCUSSION studied the foregut, he excluded the esophagus and con- The observed enzymatic activity of the hindgut has not centrated on the buccal cavity and salivary glands. This been previously reported. Both a cellobiase and an amyl- was unfortunate since our results showed a reasonably ase are present here. Specific enzymes capable of hydro¬ wide range of activity here. All the carbohydrates tested underwent some decomposition in the esophagus, also lyzing the other substrates tested also appear to be present in this part of the gut. However, it appears likely that Table 3 indicates that some of the enzymes may be the other enzymes are produced in the foregut or midgut produced here. Vol. 6; Supplement THE VELIGER Page 24 Table 6 Distribution of Reducing Sugar Formed in Situ Substrates: starch, laminarin, alginate, fucoidin, 0.1% cellobiose, 0.15% ; incubation at 15° C for 24 hours. ug Reducing Sugar Present in Lumen Substrates Anatomical Region Starch Laminarin Alginate Fucoidin Cellobiose ug Reducing Sugar 172.3 87.4 256.9 321.7 foregut 324.0 68.6 13.1 hindgut ug Reducing Sugar Present in Wall Substrates Anatomical Region Starch Laminarin Alginate Fucoidin Cellobiose ug Reducing Sugar" foregut 684.5 hindgut 152.8 0 corrected by subtraction of substrate control. corrected by subtraction of tissue control. SUMMARY LITERATURE CITED Carbohydrate digestion in the snail Tegula funebralis BLACK, W. A. P., W. J. CORNHELL, E. T DEWAR & E N. WOODWARD (A. ADAMS, 1854), was studied. The intestinal sites of 1951. Manufacture of algal chemicals: Laboratory-scale iso¬ hydrolysis of certain carbohydrates and the location of lation of Laminarin from brown marine algae. Journ. appl. production of their respective enzymes were studied. Chem. 1: 505 -517 The presence of an amylase, laminarase, alginase, fuco¬ BLACK, W. A. P., E. T. DEWAR & F N. WOODWARD idase, and cellobiase was demonstrated. The major tissue 1952. Manufacture of algal chemicals: Laboratory-scale iso¬ sources of the above enzymes were: buccal cavity, stom¬ lation of Fucoidin from brown marine algae. Journ. Sci. of Food and Agricult. 3: 122 - 129 ach, digestive gland, spiral caecum, thin and thick hindgut for amylase; buccal cavity and esophagus for laminarase GALLI, DONALD RICHARD and alginase; buccal cavity, esophagus, stomach and 1956. Carbohydrate digestion in a herbivorous marine snail, digestive gland for fucoidase; salivary glands, spiral Tegula funebralis. Master of Arts Thes., Stanford Univ.; 153 pages caecum, thin and thick hindgut for cellobiase. Some of the carbohydrate hydrolysis appears to be due to bacterial action. Intracellular digestion of starch in the wall of the hindgut is indicated. Page 25 Vol. 6; Supplement THE VELIGER A New Pigment from Tegula funebralis (Mollusca: Gastropoda) PATRICIA MCGEE Hopkins Marine Station of Stanford University, Pacific Grove, California (1 Text figure; 3 Tables) change. Prolonged heating at 100° C resulted in a brown IN THE TROCHACEAN SPECIES Tegula funebralis (A. discoloration, and is assumed to be due to decomposition. ADAMS, 1854) and T. brunnea (PHILIPPI, 1848) which It is photosensitive, and becomes yellow with prolonged are abundant in the intertidal zone of the Pacific coast, exposure to light. When reduced with hydrosulfite, a yel- the female gonad is bright green. In both species, the low color appears, but reoxidation to green can be achieved pigment is found in droplets evenly dispersed throughout by autoxidation or treatment with H.O2. In methanol, the volk. An extraction of the pigment in T. funebralis a green fluorescence was observed in the oxidized form. was made. The crude green pigment was partitioned into The large molecular size suggested a protein complex. a group of yellow carotenoids and an unknown green The unknown was, therefore, placed in aqueous solution pigment. This is a study of these colored materials. and an equal amount of CHCIs with .1 volume amylal¬ PREPARATION cohol added. This was vigorously shaken and centrifuged for 10 minutes. A blue protein appeared between the The pigment was initially extracted from eggs carefully phases of green aqueous solution and colorless CHCIa. stripped from 200 gonads. The eggs were blended in a The aqueous phase was re-treated until the blue zone no Waring blender with absolute methanol for five minutes. longer appeared. The solubilities and spectrum of the un- The methanol was changed, and extraction was repeated until the suspension was white. The crude green pigment was then dried and redissolved in methanol. This re¬ RELATIVE ABSORPTION extraction was repeated three times. Ether and water partition of the pigment separated the material into a vellow epiphase and a green hypophase. Repeated parti- 07 tioning was used to purify the materials. RESULTS The yellow material, dried and dissolved in petroleum ether (Bp. 40° 60° C) was placed on an Al-Oa column. The column was developed with a gradient of acetone in petroleum ether. The four bands observed were collected, and a tentative identification of zeaxanthin, lutein and alpha carotene was made from the data in Table I (P. KARRER & E. JUCKER, 1950). The green pigment could not be identified. Some of its 250 300 350 400 450 500 550 600 650 700 properties are briefly stated in Table II. In addition, in aqueous solution it freely passed through sephadex G-75 which indicates a molecular size larger than that cor- Figure 1: The absorption maxima of the unknown green responding to a molecular weight of 40,000. In aqueous pigment in H.O. The oxidized state peaks at 640 and 273, solution, it may be warmed to 100° C without obvious while the reduced state peaks at 273 u. Page 26 Vol. 6; Supplement THE VELIGER Table 1 PROPERTIES OF YELLOW PIGMENTS ABSORPTION CAROTENOID“ BAND MAXIMA in CS. REMARKS I 517 482 450 hypophasic in petroleum zeaxanthin ether and 90% MeÖH II 510 470 442 distributed in both phases of pet. ether and 90% MeOH III 508 475 445 hypophasic in petroleum lutein ether and 90% MeÖH a - carotene 509 477 epiphasic in petroleum ether and 90% MeÖH * Tentative identification on the basis of the absorption spectra and solubility properties. Table 2 PROPERTIES OF GREEN PIGMENT COLORATION ABSORPTION MAXIMA mu SOLUBILITY PIGMENT reduced reduced oxidized oxidized neutral¬ neutral¬ H.O s. H.O, MeOH, H.O 1. Native yellow green EtOH, acet. 640 273 273 acid¬ acid¬ eth., CHCI, MeoH vellow vellow 640 370*(s) pet. eth., alkaline- alkaline- CS. vellow yellow with ppt. same as 1 same as 1 same as 1 same as 1. same as 1 except Deproteinized alkaline- vellow with no ppt. neutral¬ neutral¬ H.O H.O s. H.O yellow- Allagochrome 630 320 260 320 260 green acid¬ orange (Habermann, acid¬? 1960) alkaline- alkaline-? brown * (s) = shoulder. s. = soluble i. = insoluble eth. = ether pet. eth. = petroleum ether acet. — acetone Page 27 Vol. 6; Supplement THE VELIGER is that coenzyme Q is necessary for respiratory electron Table 3 transfer occurring in the mitochondria and equivalent Results of mass spectral analysis of crude structures. While several quinones of biological origin have green pigment in percent by weight been described, their actual involvement in electron trans- ELEMENT PERCENT ELEMEN PERCENT port has seldom been demonstrated. If a respiratory func- tion for the unknown pigment is postulated, the observed 0.005 Al migration of the pigment to the ciliated cells of the velum Ca 0.01 0.10 of the trochophore and veliger larvae may be of signif- Cu 0.005 0.005 icance. These cells would be expected to have a high 0.01 0.01 metabolic activity. Mg 0.03 Zn trace Mn trace SUMMARY known without protein appear in Table II. It should be The pigments of the eggs of Tegula funebralis were ex¬ tracted in methanol. This crude green pigment contained noted that the absorption spectrum of the oxidized form three yellow materials with spectral properties resembling was not changed. the carotenoids: zeaxanthin, lutein and alpha carotene, In preliminary observations of the development of the and an unknown green pigment. The green pigment was closely related Tegula brunnea the green pigment present found to have an attached protein, absorption maxima in the eggs was observed to concentrate in the ciliated in H.O at 640, 273mu in the oxidized form and 273 mu cells of the trochophore. The amount appeared to in¬ in the reduced state, and a marked resemblance to known crease as the velum formed. quinones that have been suggested to act as respiratory DISCUSSION pigments. The unknown pigment resembles Allagochrome (HABER- LITERATURE CITED MANN, 1960; GARRICK & HABERMANN, 1962) in its ab¬ CRANE, F. L. sorption spectrum and oxidation-reduction activities. A 1959. Internal distribution of Coenzyme Q in higher plants. comparison of the two pigments' properties can be seen Plant Physiol. 34: 128 - 131 in Table II. Allagochrome is present in a variety of higher GARRICK, L. S. & H. M. HABERMANN plants and its function is hypothesized to be respiratory 1962. Distribution of allagochrome in vascular plants. due to the ease with which oxidation and reduction can Amer. Journ. Bot. 49: 1078 -1088 be induced HABERMANN, H. M. The peak at 273 mu also is suspiciously near the char- 1960. A new leaf pigment (pp. 73 -82 in:) Comp. Biochem. acteristic peak, 275 mu of the coenzyme Q, a lipid soluble of photoreactive systeins; Acad. Press, New York and London. quinone (CRANE, 1959). There is a broad distribution of xii + 437 pp. the five known forms of coenzyme Q in aerobic tissues KARRER, P & E. JUCKER It has been found in all vertebrates, higher plants, aerobic 1950. Caretonoids. Elsevier Publ. Co., Inc. New York etc. bacteria, invertebrates and red and green alga. The view x + 384 pp.